Inorganic-organic melt-extruded hybrid yarns and fibrous composite medical devices thereof

ABSTRACT

Composite fibrous constructs are made of combinations of inorganic-organic hybrid monofilament or multifilament yarns containing at least 6 weight percent of inorganic micro-/nanoparticles and organic monofilament or multifilament yarn with typical examples of the hybrid yarn matrix made of absorbable or non-absorbable thermoplastic polymers and final constructs being in the form of knitted or woven meshes and braided ligatures intended to perform under specific mechanically, biologically, and/or radiologically related functions.

The present application is a continuation in part of U.S. patentapplication Ser. No. 11/599,691, filed on Nov. 15, 2006, which claimsthe benefit of prior provisional application, U.S. Ser. No. 60/737,022filed on Nov. 15, 2005.

FIELD OF THE INVENTION

This invention is directed toward the use of inorganic-organicmelt-extruded hybrid yarns as part of composite fibrous medical deviceswhich can be used, among other applications, to impart radiopacity tosurgical articles and serve as carriers for the controlled release ofbioactive agents immobilized onto the inorganic components.

BACKGROUND OF THE INVENTION

Traditional melt-extruded, fine filaments of different cross-sectionalgeometries having a cross-sectional area at or below 4 mm² andparticularly those having a cross-sectional area of less than 2 mm² suchas monofilament and multifilament yarns used for manufacturing differentknitted and woven textile constructs, monofilament sutures, andmultifilament braided sutures, are known to be based on thermoplasticcrystalline polymers comprising linear chains. An exception to thetraditional practice was disclosed by one of the present inventors,wherein polyaxial polymers (with a monocentric branching point) wereprepared and converted to strong monofilaments useful for the productionof surgical sutures and allied medical products (U.S. Pat. Nos.6,462,169 and 6,794,485). It is also traditional to incorporate lessthan 2 weight percent of solid inorganic additives in textile fibers asdelustering agents (e.g., TiO₂) and to a lesser extent, colorants andheat stabilizers. And frequently, these additives tend to cluster in thepolymer melt and interfere with extrusion of articles having smallcross-sectional areas as in the case of fiber melt-spinning. In spite ofthe availability of a great number of inorganic additives that canconceptually impart unique and useful properties to extruded filaments,if used in quantities exceeding 2 weight percent, investigators of theprior art have failed to explore this option to avoid known or perceivedcomplications in the melt-spinning of such inorganic-organic hybridsystems. These facts and contemporary needs for unique hybridmicrocomposites in filament form provided a strong incentive to pursuethe study subject of the present parent patent application, which isdirected to a new family of inorganic-organic hybrid filamentscontaining at least 10 weight percent of at least one inorganiccomponent uniformly dispersed as microparticles in an organic polymericmatrix to impart one or more useful properties to medical and/orpharmaceutical devices made thereof. And the parent patent applicationdealt, in general, with a family of inorganic-organic hybridmelt-extruded filaments, which are particularly useful for theproduction of absorbable/disintegratable coil components of anabsorbable/disintegratable endoureteral stent and radiopaque markers orsutures. Clinically novel aspects of incorporating the hybrid filamentsin braided or knitted medical constructs, which can, in part, be usedfor the purpose of imparting radiopacity and/or bioactivity were notdisclosed in the parent patent application. Accordingly, these aspectsconstitute the tenets of the present application.

SUMMARY OF THE INVENTION

This invention is generally directed to a composite fibrous constructhaving at least one type of inorganic-organic hybrid melt-extruded yarn,the hybrid yarn comprising an organic thermoplastic polymeric matrixcomponent and at least about 6 percent by weight of at least one type ofinorganic micro-/nanoparticles dispersed in the polymeric matrix, thehybrid yarn having a structure selected from monofilament yarns andmultifilament yarns, and wherein at least some of the inorganicparticles are radiopaque to X-ray or radiation used in magneticresonance imaging.

A specific aspect of the invention deals with a composite fibrousconstruct as described above, wherein at least one of the bioactiveagents is selected from antimicrobial agents, anti-inflammatory agents,anesthetic agents, antineoplastic agents, antiproliferative agents andcell growth promoting agents.

Another specific aspect of this invention deals with a composite fibrousconstruct comprising at least one type of inorganic-organic hybridmelt-extruded yarn, the hybrid yarn comprising an organic thermoplasticpolymeric matrix component and at least about 6 percent by weight of atleast one type of inorganic micro-/nanoparticles dispersed in thepolymeric matrix, the hybrid yarn having a structure selected frommonofilament yarns and multifilament yarns, wherein the inorganicmicro-/nanoparticles are selected from the group consisting of oxides,carbonates of multivalent metals, sulfates of multivalent metals,phosphate salts, polymeric phosphate glasses, polymeric phosphate glassceramics, phosphate ceramics, ZrO₂, and basic bismuth carbonate, andwherein the multivalent metals are selected from the group consisting ofMg, Ca, Ba, Sr, Zr, Zn, Bi, and Fe. Meanwhile, the phosphate salts areselected from the group consisting of CaHPO₄, K₂HPO₄, KH₂PO₄, Na₂HPO₄,NaH₂PO₄, Ca₃(PO₄)₂, Ca₁₀(OH)₂(PO₄)₆, and Ca₂P₂O₇ and the polymericphosphate glasses are derived from P₂O₅, CaO, and at least one oxideselected from the group consisting of ZnO, SrO, Na₂O, K₂O, SiO₂, Fe₂O₃,and ZrO₂.

A key aspect of this invention deals with a composite fibrous constructcomprising at least one type of inorganic-organic hybrid melt-extrudedyarn, the hybrid yarn comprising an organic thermoplastic polymericmatrix component and at least about 6 percent by weight of at least onetype of inorganic micro-/nanoparticles dispersed in the polymericmatrix, the hybrid yarn having a structure selected from monofilamentyarns and multifilament yarns, wherein the organic thermoplasticpolymeric matrix comprises an absorbable polyester having chainsequences derived from at least one cyclic monomer selected from thegroup consisting of ε-caprolactone, glycolide, a lactide, p-dioxanone,1,5-dioxepan-2-one, trimethylene carbonate, and a morpholinedione, orwherein the organic thermoplastic matrix comprises an absorbablepolyether-ester. The absorbable polyether-ester is preferably apolyethylene glycol end-grafted with at least one cyclic monomerselected from the group consisting of ε-caprolactone, glycolide, alactide, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one and amorpholinedione.

Another key aspect of this invention deals with a composite fibrousconstruct as described above, wherein the organic thermoplasticpolymeric matrix comprises a non-absorbable polymer selected from thegroup consisting of Nylon 6, Nylon 12, Nylon 11, and a polyalkyleneterephthalate.

A technologically important aspect of this invention deals with acomposite fibrous construct comprising at least one type ofinorganic-organic hybrid melt-extruded yarn, the hybrid yarn comprisingan organic thermoplastic polymeric matrix component and at least about 6percent by weight of at least one type of inorganic micro-/nanoparticlesdispersed in the polymeric matrix, wherein the construct is in the formof a braid of the hybrid yarn and at least one other multifilament yarnof an organic thermoplastic polymer, and wherein the braid comprises acore comprising the hybrid yarn and a sheath made of the at least oneother multifilament yarn, the hybrid yarn comprising a monofilament.Meanwhile, the inorganic micro-/nanoparticle comprises barium sulfateand the organic thermoplastic polymeric matrix of the hybrid yarncomprises at least one polymer selected from the group consisting ofpoly-ε-caprolactone, Nylon 6, Nylon 12, and an absorbable segmentedpolyester derived from one of glycolide and l-lactide and at least oneadditional cyclic monomer. Additionally, at least one of themultifilament constituent yarns of the braid comprises an organicthermoplastic matrix selected from ultrahigh molecular weightpolyethylene, Nylon 6, Nylon 12, Nylon 11, a polyalkylene terephthalate,polypropylene, polyether-ether ketone, and an aromatic polyamide.

A clinically important aspect of this invention deals with a compositefibrous construct comprising at least one type of inorganic-organichybrid melt-extruded yarn, the hybrid yarn comprising an organicthermoplastic polymeric matrix component and at least about 6 percent byweight of at least one type of inorganic micro-/nanoparticles dispersedin the polymeric matrix, the hybrid yarn having a structure selectedfrom monofilament yarns and multifilament yarns wherein the saidconstruct is in the form of a braid of the hybrid yarn and at least oneother multifilament yarn of an organic thermoplastic polymer, andwherein the braid is coated. Furthermore, the coating contains at leastone bioactive agent selected from antimicrobial agents, antiviralagents, anesthetic agents, anti-inflammatory agents, antineoplasticagents and cell growth promoting agents.

Another clinically important aspect of this invention deals with acomposite fibrous construct comprising at least one type ofinorganic-organic hybrid melt-extruded yarn, the hybrid yarn comprisingan organic thermoplastic polymeric matrix component and at least about 6percent by weight of at least one type of inorganic micro-/nanoparticlesdispersed in the polymeric matrix, the hybrid yarn having a structureselected from monofilament yarns and multifilament yarns wherein thesaid construct is in the form of knitted or woven mesh comprising acombination the hybrid yarn and at least one other multifilament yarn ofan organic polymer, the hybrid yarn comprising a multifilament yarn, andwherein the mesh is used for hernial repair. Meanwhile, the mesh furthercomprises a lubricious coating wherein the coating contains at least onebioactive agent selected from antimicrobial agents, antiviral agents,anesthetic agents, anti-inflammatory agents, antineoplastic agents andcell growth promoting agents.

Another aspect of this invention that is of great clinical significancedeals with a composite fibrous construct comprising at least one type ofinorganic-organic hybrid melt-extruded yarn, the hybrid yarn comprisingan organic thermoplastic polymeric matrix component and at least about 6percent by weight of at least one type of inorganic micro-/nanoparticlesdispersed in the polymeric matrix, the hybrid yarn having a structureselected from monofilament yarns and multifilament yarns wherein thesaid construct is in the form of a high strength suture or ligature fortissue repair.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The parent patent application provided a clear dispute to the commonbelief that incorporation of more than about 2 weight percent ofinorganic additives for imparting value-added properties tomelt-extrudable fiber-forming polymers impairs their conversion intofilaments having cross-sectional areas such as those varying between100μ² and 4 mm². In effect, the parent case is directed to hybridinorganic-organic compositions comprising at least 10 weight percent ofan inorganic component present as uniformly dispersedmicro-/nanoparticles in absorbable or non-absorbable organic polymericmatrices, which were converted under controlled extrusion conditions tofilaments having wide ranges of cross-sectional areas and geometries.The resulting filaments were described as useful components forconstructing several forms of medical devices. Recognition of thetechnological significance of the hybrid inorganic-organic filamentsprovided an incentive to explore their incorporation in unique compositefibrous constructs targeted for use in specific contemporary medicalapplications. And this broadened the scope of hybrid filament productionto include monofilament and multifilament yarns of traditionaldimensions as those used in braided and knitted textile constructs,widely used in the medical industry. Additionally, this invention dealswith the formation of continuous hybrid microfilaments for use asradiological markers and filling scaffolds in diseased blood capillariesand vessels in place of currently used metallic microfilaments. Usingdifferently formed constructs containing hybrid microfibers or yarns inradiological applications entails those associated with X-ray andmagnetic resonance imaging. A unique application of these radiologicalmarkers can be associated with (1) locating and monitoring treated tumorsites; (2) their incorporation in high load-bearing devices, such as inhernial meshes and orthopedic ligatures, for timely detection ofmechanical failure of these devices or at the device-tissue interface;(3) monitoring tissue ingrowth, unexpected deformation or dimensionalchanges at surgical sites or diseased organs; (4) providing guidanceduring biopsy procedures; and (5) monitoring the physical collapse ofabsorbable structural devices, which may contain bioactive agents neededduring their presence at biological sites. Another aspect of the presentinvention deals with the use of the inorganic particles in the hybridfilaments as carriers of bioactive agents with specific biologicalactivities depending on the type of sought treatment at the applicationsite. The bioactive agents can be immobilized on the surface of theparticles and diffuse outwardly through the absorbable or non-absorbablematrix. It is also possible that as the absorbable filament matrixabsorbs, thus releasing the activated particles, the active agentsbecome more bioavailable. Furthermore, part of the agent(s) can be alsoincorporated in the organic matrix of the hybrid filament to providemore than one release profile of said agent(s). A specific aspect ofthis invention deals with absorbable or bioactive particles in anabsorbable matrix wherein the bioactive particles become available totissue at the implantation site when the polymeric matrix absorbs.Typical illustrations of this situation are associated with bone orcartilage regeneration and tissue engineering.

Further illustrations of the present invention are provided by thefollowing examples:

EXAMPLE 1 Synthesis of a Segmented Polyaxial CopolyesterGlycolide/Caprolactone/Trimethylene Carbonate (G/C/TMC) with 35% BaSO₄by Weight

The reaction apparatus comprised a 1L stainless steel kettle with a3-neck glass lid equipped with an overhead mechanical stirring unit,vacuum adapter, and two nitrogen inlets. An initial charge of 9.1 g. ofa polyaxial trimethylene carbonate as polymeric initiator (preparedaccording to U.S. Pat. No. 6,794,364) and 245 g. of predried bariumsulfate was added to the kettle. The initial charge also consisted of132.1 g. (1.1592 moles) ε-caprolactone, 313.8 g. (2.7048 moles)glycolide. The apparatus was assembled and maintained under reducedpressure at room temperature for at least 20 minutes. The apparatus andits contents were lowered into a high temperature oil bath that waspreheated to 40° C.

The system was then purged with nitrogen and the temperature of the oilbath was increased to 95° C. Once the apparatus was purged with nitrogenthe vacuum adaptor was removed and a stir bearing was put in its placeand stirring at 60 RPM was started. When the monomers appeared meltedand well mixed, 2.576 mL of a 0.2M stannous octanoate catalyst solutionin toluene (5.152×10⁻⁴ moles) was added to the kettle. The temperaturewas increased to 180° C. As the polymerization charge gradually becamemore viscous, the stirring was slowed proportionally until the chargebecame too viscous to stir, the stirring was stopped. The reaction wasmaintained at 180° C. for 7 hours.

The polymer was frozen so that it could be removed and ground. Theground material was transferred to a 2L pear shaped glass flask andplaced on a Buchi Rotavapor. After achieving a vacuum of 0.25 mm Hg, theflask was lowered into an oil bath. The temperature was raised to 40° C.After 2 hours at 40° C., the temperature of the oil bath was increasedto 80° C. After 1 hour at 80° C., the temperature was increased to 110°C., and maintained at this temperature for 4 hours.

The inherent viscosity, using hexafluoroisopropanol (HFIP) as a solventand separating the BaSO₄, was 1.1 dl/g. The melting temperature and heatof fusion, as determined by differential scanning calorimetry, were 223°C. and 54 J/g, respectively.

EXAMPLE 2 Synthesis of 35-65 by Weight BaSO₄—Poly-ε-Caprolactone (PCLB)

A reaction apparatus similar to that described in Example 1 was used forthe synthesis of PCLB. Following a procedure similar to that describedin Example 1, the initial charge of 0.2708 g. (3.56×10⁻³ moles) ofpropanediol, 650 g. (5.70175 moles) ε-caprolactone, and 245 g. predriedbarium sulfate was added to the kettle. The assembled apparatus wasplaced under reduced pressure and lowered into an oil bath that waspreheated to 50° C.

The system was then purged with nitrogen and the oil bath temperaturewas increased to 120° C. Once the apparatus was purged with nitrogen2.576 mL of a stannous octanoate catalyst, 0.2M solution in toluene(5.152×10⁻⁴ moles) was added to the kettle. The vacuum adaptor wasremoved and a stir bearing was put in its place and stirring at 140 RPMwas started. The temperature was maintained at 120° C. for 15 minutesthen increased to 160 C. As the polymerization charge gradually becamemore viscous, the stir was slowed proportionally until the polymerbecame too viscous to stir, the stirring was stopped. The reaction wasmaintained at 160° C. for 6 hours from the time the stir was stopped.

The polymer was isolated, ground, and dried at 40° C. under reducedpressure. Residual monomer was distilled by heating under reducedpressure until a constant weight is achieved.

The inherent viscosity, using chloroform (CHCl₃) as a solvent andfiltering the BaSO₄, was 1.41 dl/g. The melting temperature and heat offusion, as determined by differential scanning calorimetry, were 67° C.and 78 J/g, respectively. The molecular weight, M_(n), M_(w), and PDI,as determined by GPC using dichloromethane, were 107.7 kDa, 190.2 kDa,and 1.77, respectively.

EXAMPLE 3 Monofilament Fiber Extrusion of MG5B from Example 1

A single screw extruder with four zones was used to extrude the polymerinto a monofilament. The polymer was extruded using a 0.6 mm die. A 325line per inch filter pack was used. Zone 1 was maintained at 100° C.Zone 2 was maintained at 205° C. Zone 3 was maintained at 220° C. SpinPack was maintained at 225° C. The pump was maintained at 215° C. Themetering pump was also operated at 8 rpm while the take up roll was setbetween 53 and 56 rpm. The collected monofilament had diameters between0.69 mm and 0.59 mm. The fiber was drawn at 4.1× in the first stage at60° C. and 0.2× in the second stage at 70° C. resulting in a diameter of0.36 mm. The resulting fiber had a maximum load of 22.2N, a strength of31.7 Kpsi, a modulus of 259 Kpsi, and elongation of 26.3%. The freeshrinkage was 10.4%.

EXAMPLE 4 Monofilament Fiber Extrusion of PCLB from Example 2

A single screw extruder with four zones is used to extrude the polymerinto a monofilament. The polymer is extruded using a 0.6 mm die and a325 line per inch filter pack. The heat is set as follows for Zones 1,2, 3, pump, and spin pack, 45° C., 55° C., 60° C., 69° C., and 68° C.,respectively, and adjusted accordingly. The metering pump is initiallyset at 8 rpm and the take up roll will be set to 65 rpm and adjusted toachieve the desired diameter. The collected monofilaments havingdiameters between 0.8 mm and 0.5 mm are oriented by drawing to adiameter of 0.28-0.38 mm.

EXAMPLE 5 Composite Braid (GB) Construction of Ultrahigh MolecularWeight Polyethylene and Monofilament Yarn of Example 3: GeneralProcedure

Initially, ultrahigh molecular weight polyethylene (UHMW-PE)multifilament was plied using a Simet plying unit. The composite braid(GB) constructions required either a single-ply or triple-ply of UHMW-PEmultifilament. Next a predetermined amount of UHMW-PE multifilament waswound onto spools using a Herzog SP02 winding unit. These spools werethen placed onto either a Herzog RU 2/12-80 or 2/16-80 braiding unit tobe used as the sheath of the GB braid. Meanwhile, the cores of thebraids were prepared using either a single-ply or triple-plymonofilament of hybrid monofilament, MG5B. For the single-ply core, themonofilament was wound onto a spool using the Herzog SP02 winder. Thisspool was then loaded into the appropriate braider by placing it on atensioning unit located underneath the braider. The monofilament wasthen fed upwards and joined with the UHMW-PE spools. When a triple plywas used, the monofilament was wound onto three separate spools usingthe Herzog SP02 winder. These spools were then loaded into a singletrack on the Herzog RU2/12-80 braider and twisted. Subsequently, thetwisted monofilaments were loaded onto the braider using the same methodas previously described with the single monofilament core. Afterbraiding, the braid was tightened by threading through an open airheating oven at predetermined through put and tension.

EXAMPLE 6 Construction and Comparative Tensile Properties of ThreeComposite Braids Made According to Example 5

Braids GB-1a and GB-1b, described in Table I, were constructed using TO9285-01 Dyneema Purity Low Creep (UG) dtex440 TS60 and a core of singleMG5B monofilament. Braid GB-2a was constructed using TO 9285-01 DyneemaPurity Low Creep (UG) dtex440 TS60 and a core of triple-ply MG5Bmonofilament. Braids GB-3a and GB-3b were constructed using TO 9285-02Dyneema Purity SGX dtex220 TS80 and a core of triple-ply MG5Bmonofilament.

TABLE I Constructions of GB Composite Braids and Their TensileProperties Tensile Properties Construction Diameter Breaking Braid #Sheath Core Picks Per Inch (mm) Strength (N) GB-1a 12^(a) 1^(a) 51.261.2 560 GB-1b 12^(a) 1 (3-ply) 50.11 1.3 655 GB-2a 12^(a) 1 (3-ply)50.11 1.2 500 GB-3a 16 1 (3-ply) 29.79 1.8 1410 (3-ply) GB-3b 16 1(3-ply) 11.02 1.6 1050 (3-ply) ^(a)Single monofilament

EXAMPLE 7 Synthesis of 35/65 by Weight of Barium Sulfate (BaSO₄)/Nylon 6(N6-B)

A predried stainless steel reactor equipped for mechanical stirring andwith inlets for introducing dry nitrogen or applying vacuum is used toprepare N6-B. The reactor is charged with a mixture of □-caprolactam(113 g, 1 mole), 6-aminocaproic acid (1.31 g., 10 mmole) and predriedbarium sulfate microparticles (61.5 g.). The reactor is purged with drynitrogen and the polymerization charge is heated under a positivenitrogen atmosphere to about 80° C. to completely melt the caprolactam.The reactants are then heated to 220° C. while stirring to ensureadequate dispersion of the BaSO₄ microparticles. Upon reaching 220° C.,the stirring is continued until the polymerization charge becomes tooviscous to stir (about 4 hours). At this point, the stirring is stoppedand the polymerization temperature is raised to 255° C. and the reactionis continued under a positive nitrogen atmosphere for about 20 hours,and subsequently, at 760 mm pressure for an additional 5 hours, and thenat 260° C. for 2 hours. To complete the polymerization, the charge isheated at 230° C. for 30 minutes under reduced pressure (˜2 mm). Theresulting composite system is cooled to room temperature, removed, andground. The ground product is extracted with water in a Soxhlet extruderfor 2 days, dried at 70° C. for 4 hours, and then at 110° C. until aconstant weight is achieved.

EXAMPLE 8 Synthesis of 35/65 by Weight of Barium Sulfate (BaSO₄)/Nylon12 (N12-B)

Using a similar method to that used in Example 7, N12-B is prepared (1)using an initial charge of laurolactam (197 g., 1 mole) and 18% aqueousphosphoric acid (12 mL) and BaSO₄ (106 g.); (2) heating to about 155° C.to melt the monomer; (3) heating under positive nitrogen pressureaccording to the following temperature ° C./time (hours) scheme: 160/2,190/3, 265/20; (4) heating at 760 mm and 260° C. for 2 hours; and (5)heating under reduced pressure (2 mm) and 230° C. for 0.5 hours. Theproduct is isolated and ground. The unreacted monomer is removed bydistillation by heating under vacuum. Traces of residual monomer areextracted with 2-propanol. The extracted polymer is dried at 80° C.under vacuum until a constant weight is achieved.

Although the present invention has been described in connection with thepreferred embodiments, it is to be understood that modifications andvariations may be utilized without departing from the principles andscope of the invention, as those skilled in the art will readilyunderstand. Accordingly, such modifications may be practiced within thescope of the following claims. Moreover, Applicants hereby disclose allsubranges of all ranges disclosed herein. These subranges are alsouseful in carrying out the present invention.

1. A composite fibrous construct comprising at least one type ofinorganic-organic hybrid melt-extruded yarn, the hybrid yarn comprisingan organic thermoplastic polymeric matrix component and at least about 6percent by weight of at least one type of inorganic micro-/nanoparticlesdispersed in the polymeric matrix, the hybrid yarn having a structureselected from monofilament yarns and multifilament yarns.
 2. A compositefibrous construct as set forth in claim 1 wherein at least some of theinorganic particles are radiopaque to X-ray or radiation used inmagnetic resonance imaging.
 3. A composite fibrous construct as setforth in claim 1 wherein at least some of the inorganic particles carryat least one bioactive agent.
 4. A composite fibrous construct as setforth in claim 3 wherein at least one of the bioactive agents isselected from antimicrobial agents, anti-inflammatory agents, anestheticagents, antineoplastic agents, antiproliferative agents and cell growthpromoting agents.
 5. A composite fibrous construct as set forth in claim1 wherein the inorganic micro-/nanoparticles are selected from the groupconsisting of oxides, carbonates of multivalent metals, sulfates ofmultivalent metals, phosphate salts, polymeric phosphate glasses,polymeric phosphate glass ceramics, phosphate ceramics, ZrO₂, and basicbismuth carbonate.
 6. A composite fibrous construct as set forth inclaim 5 wherein the multivalent metals are selected from the groupconsisting of Mg, Ca, Ba, Sr, Zr, Zn, Bi, and Fe.
 7. A composite fibrousconstruct as set forth in claim 5 wherein the phosphate salts areselected from the group consisting of CaHPO₄, K₂HPO₄, KH₂PO₄, Na₂HPO₄,NaH₂PO₄, Ca₃(PO₄)₂, Ca₁₀(OH)₂(PO₄)₆, and Ca₂P₂O₇.
 8. A composite fibrousconstruct as set forth in claim 5 wherein the polymeric phosphateglasses are derived from P₂O₅, CaO, and at least one oxide selected fromthe group consisting of ZnO, SrO, Na₂O, K₂O, SiO₂, Fe₂O₃, and ZrO₂.
 9. Acomposite fibrous construct as set forth in claim 1 wherein the organicthermoplastic polymeric matrix comprises an absorbable polyester havingchain sequences derived from at least one cyclic monomer selected fromthe group consisting of ε-caprolactone, glycolide, a lactide,p-dioxanone, 1,5-dioxepan-2-one, trimethylene carbonate, and amorpholinedione.
 10. A composite fibrous construct as set forth in claim1 wherein the organic thermoplastic matrix comprises an absorbablepolyether-ester.
 11. A composite fibrous construct as set forth in claim10 wherein the absorbable polyether-ester comprises a polyethyleneglycol end-grafted with at least one cyclic monomer selected from thegroup consisting of ε-caprolactone, glycolide, a lactide, trimethylenecarbonate, p-dioxanone, 1,5-dioxepan-2-one and a morpholinedione.
 12. Acomposite fibrous construct as set forth in claim 1 wherein the organicthermoplastic polymeric matrix comprises a non-absorbable polymerselected from the group consisting of Nylon 6, Nylon 12, Nylon 11, and apolyalkylene terephthalate.
 13. A composite fibrous construct as setforth in claim 1 in the form of a braid of the hybrid yarn and at leastone other multifilament yarn of an organic thermoplastic polymer.
 14. Acomposite fibrous construct as set forth in claim 13 wherein the braidcomprises a core comprising the hybrid yarn and a sheath made of the atleast one other multifilament yarn, the hybrid yarn comprising amonofilament.
 15. A composite fibrous construct as set forth in claim 14wherein the inorganic micro-/nanoparticle comprises barium sulfate andthe organic thermoplastic polymeric matrix of the hybrid yarn comprisesat least one polymer selected from the group consisting ofpoly-ε-caprolactone, Nylon 6, Nylon 12, and an absorbable segmentedpolyester derived from one of glycolide and l-lactide and at least oneadditional cyclic monomer.
 16. A composite fibrous construct as setforth in claim 15 wherein the at least one other multifilament yarncomprises an organic thermoplastic matrix selected from ultrahighmolecular weight polyethylene, Nylon 6, Nylon 12, Nylon 1, apolyalkylene terephthalate, polypropylene, polyether-ether ketone, andan aromatic polyamide.
 17. A composite fibrous construct as set forth inclaim 13 wherein the braid is coated.
 18. A composite fibrous constructas set forth in claim 17 wherein the coating contains at least onebioactive agent selected from antimicrobial agents, antiviral agents,anesthetic agents, anti-inflammatory agents, antineoplastic agents andcell growth promoting agents.
 19. A composite fibrous construct as setforth in claim 1 in the form of knitted or woven mesh comprising acombination the hybrid yarn and at least one other multifilament yarn ofan organic polymer, the hybrid yarn comprising a multifilament yarn. 20.A composite fibrous construct as set forth in claim 19 wherein the meshis used for hernial repair.
 21. A composite fibrous construct as setforth in claim 20 wherein the mesh further comprises a lubriciouscoating.
 22. A composite fibrous construct as set forth in claim 21wherein the coating contains at least one bioactive agent selected fromantimicrobial agents, antiviral agents, anesthetic agents,anti-inflammatory agents, antineoplastic agents and cell growthpromoting agents.
 23. A composite fibrous construct as set forth inclaim 1 in the form of a high strength suture or ligature for tissuerepair.